The 'LSVEC problem' for the Vienna Peedee belemnite carbon isotope-delta scale.

Since 2016 there have been intense discussions within several established communities and networks regarding the consequences of the withdrawal of the LSVEC lithium carbonate reference material for carbon isotope-delta measurement calibration. These include the Isotope Ratio Working Group (IRWG) of the Consultative Committee for the Amount of Substance (CCQM, French: Comité Consultatif pour la Quantité de Matière) of the International Committee of Weights and Measures (CIPM, French: Comité International des Poids et Mesures); participants within the 2016, 2021 and 2024 Technical Meetings on International Atomic Energy Agency (IAEA) stable isotope ratio reference products; and the International Union of Pure and Applied Chemistry's Commission on Isotopic Abundances and Atomic Weights (IUPAC CIAAW) amongst others. The reasons for these intensive discussions relate to the privileged position that LSVEC has occupied for traceability of carbon isotope-delta measurements relative to Vienna Peedee belemnite (VPDB) and the potential implications of its withdrawal for all current and future measurements of carbon isotope-delta values.

Re-determination of R(C/C) for Vienna Peedee belemnite (VPDB).

Rationale: The isotope ratio for the internationally agreed but virtual zero-point of the carbon isotope-delta scale, Vienna Peedee belemnite (VPDB), plays a critical role in linking carbon isotope delta values to the SI. It is also a quantity used for various data processing procedures including 'O correction', clumped isotope analysis and conversion of carbon isotope delta values into other expressions of isotopic composition. A value for R(C/C) with small uncertainty is therefore desirable to facilitate these procedures.

Perspective: Hidden biases in isotope delta results and the need for comprehensive reporting.

Measurements of stable-isotope composition on an isotope-delta scale can be subject to bias between laboratories or over time within a single laboratory. This bias can arise not just from differences in method protocol but also from changes in reporting guidelines, or even to the isotope-delta scales themselves. Without a clear description of method protocols, including all sample preparation steps, instrumental parameters and settings, data processing including calibration of results and estimation of measurement uncertainty, the traceability and comparability of isotope-delta values cannot be assured as bias(es) may remain hidden.

Guidance for characterization of in-house reference materials for light element stable isotope analysis.

Rationale: Preparation of in-house reference materials (RMs) is an important aspect of light element stable isotope analysis. While some relevant information is available, there is as yet no clear set of guidelines available covering all aspects of in-house production and characterization of RMs.

Methods: To address this need, the experience of production of certified reference materials under accreditation to ISO 17034:2016 and ISO/IEC 17025:2017 has been distilled into guidance for production of in-house RMs that are fit-for-purpose.

Recalculation of stable isotope expressions for HCNOS: EasyIsoCalculator.

Rationale: The stable HCNOS isotope compositions can be reported as (a) the isotope ratio of two stable isotopes (R); (b) the isotope delta value (δ); and (c) the atom fraction of the isotopes (x). Recalculations between these different expressions are needed frequently and require the use of the absolute isotope ratio for the zero points of the stable isotope delta scales (R). The inconsistent use of R values may lead to a discrepancy in recalculated results.

Food Matrix Reference Materials for Hydrogen, Carbon, Nitrogen, Oxygen, and Sulfur Stable Isotope-Ratio Measurements: Collagens, Flours, Honeys, and Vegetable Oils.

An international project developed, quality-tested, and measured isotope-delta values of 10 new food matrix reference materials (RMs) for hydrogen, carbon, nitrogen, oxygen, and sulfur stable isotope-ratio measurements to support food authenticity testing and food provenance verification. These new RMs, USGS82 to USGS91, will enable users to normalize measurements of samples to isotope-delta scales. The RMs include (i) two honeys from Canada and tropical Vietnam, (ii) two flours from C3 (rice) and C4 (millet) plants, (iii) four vegetable oils from C3 (olive, peanut) and C4 (corn) plants, and (iv) two collagen powders from marine fish and terrestrial mammal origins.

Absolute isotope ratios defining isotope scales used in isotope ratio mass spectrometers and optical isotope instruments.

Rationale: The isotope delta is calculated from the isotope ratio of a sample and the absolute isotope ratio of the zero reference point defining each stable isotope international scale (R ). Therefore, R requires accurate determination. However, the literature contains a large number of R values, and selection of different R may lead to inconsistency in reporting and recalculating stable isotope results.

Systematic comparison of post-column isotope dilution using LC-CO-IRMS with qNMR for amino acid purity determination.

Determination of the purity of a substance traceable to the International System of Units (SI) is important for the production of reference materials affording traceability in quantitative measurements. Post-column isotope dilution using liquid chromatography-chemical oxidation-isotope ratio mass spectrometry (ID-LC-CO-IRMS) has previously been suggested as a means to determine the purity of organic compounds; however, the lack of an uncertainty budget has prevented assessment of the utility this approach until now. In this work, the previously published ID-LC-CO-IRMS methods have not only been improved by direct gravimetric determination of the mass flow of C-labelled spike but also a comprehensive uncertainty budget has been established.

Practical and theoretical considerations for the determination of δ C values of methylmercury in the environment.

Rationale: Analytical methods that can identify the source and fate of mercury and organomercury compounds are likely to be useful tools to investigate mercury in the environment. Carbon isotope ratio analysis of methylmercury (MeHg) together with mercury isotope ratios may offer a robust tool to study environmental cycling of organomercury compounds within fish tissues and other matrices.

Methods: MeHg carbon isotope ratios were determined by gas chromatography/combustion-isotope ratio mass spectrometry (GC/C-IRMS) either directly or following derivatization using sodium tetraethylborate.

Lessons learned from inter-laboratory studies of carbon isotope analysis of honey.

Forensic application of carbon isotope ratio measurements of honey and honey protein to investigate the degree of adulteration with high fructose corn syrup or other C plant sugars is well established. These measurements must use methods that exhibit suitable performance criteria, particularly with regard to measurement uncertainty and traceability - low levels of adulteration can only be detected by methods that result in suitably small measurement uncertainties such that differences of 1‰ or less can be reliably detected. Inter-laboratory exercises are invaluable to assess the state-of-the art of measurement capabilities of laboratories necessary to achieve such performance criteria.

Global spatial distributions of nitrogen and carbon stable isotope ratios of modern human hair.

Rationale: Natural stable carbon (δ(13)C) and nitrogen isotope ratios (δ(15)N) of humans are related to individual dietary habits and environmental and physiological factors. In forensic science the stable isotope ratios of human remains such as hair and nail are used for geographical allocation. Thus, knowledge of the global spatial distribution of human δ(13)C and δ(15)N values is an essential component in the interpretation of stable isotope analytical results.

Investigation of mass dependence effects for the accurate determination of molybdenum isotope amount ratios by MC-ICP-MS using synthetic isotope mixtures.

Methodology for absolute Mo isotope amount ratio measurements by multicollector inductively coupled plasma-mass spectrometry (MC-ICP-MS) using calibration with synthetic isotope mixtures (SIMs) is presented. For the first time, synthetic isotope mixtures prepared from seven commercially available isotopically enriched molybdenum metal powders ((92)Mo, (94)Mo, (95)Mo, (96)Mo, (97)Mo, (98)Mo, and (100)Mo) are used to investigate whether instrumental mass discrimination of Mo isotopes in MC-ICP-MS is consistent with mass-dependent isotope distribution. The parent materials were dissolved and mixed as solutions to obtain mixtures with accurately known isotope amount ratios.

Calibration strategies for the determination of stable carbon absolute isotope ratios in a glycine candidate reference material by elemental analyser-isotope ratio mass spectrometry.

We report a methodology for the determination of the stable carbon absolute isotope ratio of a glycine candidate reference material with natural carbon isotopic composition using EA-IRMS. For the first time, stable carbon absolute isotope ratios have been reported using continuous flow rather than dual inlet isotope ratio mass spectrometry. Also for the first time, a calibration strategy based on the use of synthetic mixtures gravimetrically prepared from well characterised, highly (13)C-enriched and (13)C-depleted glycines was developed for EA-IRMS calibration and generation of absolute carbon isotope ratio values traceable to the SI through calibration standards of known purity.

Comparison of liquid chromatography-isotope ratio mass spectrometry (LC/IRMS) and gas chromatography-combustion-isotope ratio mass spectrometry (GC/C/IRMS) for the determination of collagen amino acid δ13C values for palaeodietary and palaeoecological reconstruction.

Results are presented of a comparison of the amino acid (AA) δ(13)C values obtained by gas chromatography-combustion-isotope ratio mass spectrometry (GC/C/IRMS) and liquid chromatography-isotope ratio mass spectrometry (LC/IRMS). Although the primary focus was the compound-specific stable carbon isotope analysis of bone collagen AAs, because of its growing application for palaeodietary and palaeoecological reconstruction, the results are relevant to any field where AA δ(13)C values are required. We compare LC/IRMS with the most up-to-date GC/C/IRMS method using N-acetyl methyl ester (NACME) AA derivatives.